627 research outputs found

    Kinetics of Asymmetric Transfer Hydrogenation, Catalyst Deactivation, and Inhibition with Noyori Complexes As Revealed by Real-Time High-Resolution FlowNMR Spectroscopy

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    Catalytic hydrogen transfer from basic isopropyl alcohol to aryl ketones mediated by [(arene)­(TsDPEN)­RuCl] complexes has been investigated by operando <sup>1</sup>H NMR spectroscopy using a recirculating flow setup. Selective excitation pulse sequences allowed fast and quantitative monitoring of the key [(mesitylene)­(TsDPEN)­RuH] intermediate during catalysis, which is shown to interact with both substrates by polarization transfer experiments. Comparison of reaction profiles with catalyst speciation traces in conjunction with reaction progress kinetic analysis using variable time normalization and kinetic modeling showed the existence of two independent catalyst deactivation/inhibition pathways: whereas excess base exerted a competitive inhibition effect on the unsaturated catalyst intermediate, the active hydride suffered from an inherent first-order decay that is not evident in early stages of the reaction where turnover is fast. Isotopic labeling revealed arene loss to be the entry point into deactivation pathways to Ru nanoparticles via hydride-bridged intermediates

    Clastic Polygonal Networks Around Lyot Crater, Mars: Possible Formation Mechanisms From Morphometric Analysis

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    Polygonal networks of patterned ground are a common feature in cold-climate environments. They can form through the thermal contraction of ice-cemented sediment (i.e. formed from fractures), or the freezing and thawing of ground ice (i.e. formed by patterns of clasts, or ground deformation). The characteristics of these landforms provide information about environmental conditions. Analogous polygonal forms have been observed on Mars leading to inferences about environmental conditions. We have identified clastic polygonal features located around Lyot crater, Mars (50°N, 30°E). These polygons are unusually large (> 100 m diameter) compared to terrestrial clastic polygons, and contain very large clasts, some of which are up to 15 metres in diameter. The polygons are distributed in a wide arc around the eastern side of Lyot crater, at a consistent distance from the crater rim. Using high-resolution imaging data, we digitised these features to extract morphological information. These data are compared to existing terrestrial and Martian polygon data to look for similarities and differences and to inform hypotheses concerning possible formation mechanisms. Our results show the clastic polygons do not have any morphometric features that indicate they are similar to terrestrial sorted, clastic polygons formed by freeze-thaw processes. They are too large, do not show the expected variation in form with slope, and have clasts that do not scale in size with polygon diameter. However, the clastic networks are similar in network morphology to thermal contraction cracks, and there is a potential direct Martian analogue in a sub-type of thermal contraction polygons located in Utopia Planitia. Based upon our observations, we reject the hypothesis that polygons located around Lyot formed as freeze-thaw polygons and instead an alternative mechanism is put forward: they result from the infilling of earlier thermal contraction cracks by wind-blown material, which then became compressed and/or cemented resulting in a resistant fill. Erosion then leads to preservation of these polygons in positive relief, while later weathering results in the fracturing of the fill material to form angular clasts. These results suggest that there was an extensive area of ice-rich terrain, the extent of which is linked to ejecta from Lyot crater

    BIIL 284 reduces neutrophil numbers but increases P. aeruginosa bacteremia and inflammation in mouse lungs

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    Background: A clinical study to investigate the leukotriene B4 (LTB4)-receptor antagonist BIIL 284 in cystic fibrosis (CF) patients was prematurely terminated due to a significantly increased risk of adverse pulmonary events. We aimed to establish the effect of BIIL284 in models of Pseudomonas aeruginosa lung infection, thereby contributing to a better understanding of what could have led to adverse pulmonary events in CF patients. Methods: P. aeruginosa DNA in the blood of CF patients during and after acute pulmonary exacerbations and in stable patients with non-CF bronchiectasis (NCFB) and healthy individuals was assessed by PCR. The effect of BIIL 284 treatment was tested in an agar bead murine model of P. aeruginosa lung infection. Bacterial count and inflammation were evaluated in lung and other organs. Results: Most CF patients (98%) and all patients with NCFB and healthy individuals had negative P. aeruginosa DNA in their blood. Similarly, the P. aeruginosa-infected mice showed bacterial counts in the lung but not in the blood or spleen. BIIL 284 treatment decreased pulmonary neutrophils and increased P. aeruginosa numbers in mouse lungs leading to significantly higher bacteremia rates and lung inflammation compared to placebo treated animals. Conclusions: Decreased airway neutrophils induced lung proliferation and severe bacteremia in a murine model of P. aeruginosa lung infection. These data suggest that caution should be taken when administering anti-inflammatory compounds to patients with bacterial infections

    Asteroseismology of red giants & galactic archaeology

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    Red-giant stars are low- to intermediate-mass (M10M \lesssim 10~M_{\odot}) stars that have exhausted hydrogen in the core. These extended, cool and hence red stars are key targets for stellar evolution studies as well as galactic studies for several reasons: a) many stars go through a red-giant phase; b) red giants are intrinsically bright; c) large stellar internal structure changes as well as changes in surface chemical abundances take place over relatively short time; d) red-giant stars exhibit global intrinsic oscillations. Due to their large number and intrinsic brightness it is possible to observe many of these stars up to large distances. Furthermore, the global intrinsic oscillations provide a means to discern red-giant stars in the pre-helium core burning from the ones in the helium core burning phase and provide an estimate of stellar ages, a key ingredient for galactic studies. In this lecture I will first discuss some physical phenomena that play a role in red-giant stars and several phases of red-giant evolution. Then, I will provide some details about asteroseismology -- the study of the internal structure of stars through their intrinsic oscillations -- of red-giant stars. I will conclude by discussing galactic archaeology -- the study of the formation and evolution of the Milky Way by reconstructing its past from its current constituents -- and the role red-giant stars can play in that.Comment: Lecture presented at the IVth Azores International Advanced School in Space Sciences on "Asteroseismology and Exoplanets: Listening to the Stars and Searching for New Worlds" (arXiv:1709.00645), which took place in Horta, Azores Islands, Portugal in July 201

    Evidence for a mixed mass composition at the `ankle' in the cosmic-ray spectrum

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    We report a first measurement for ultra-high energy cosmic rays of the correlation between the depth of shower maximum and the signal in the water Cherenkov stations of air-showers registered simultaneously by the fluorescence and the surface detectors of the Pierre Auger Observatory. Such a correlation measurement is a unique feature of a hybrid air-shower observatory with sensitivity to both the electromagnetic and muonic components. It allows an accurate determination of the spread of primary masses in the cosmic-ray flux. Up till now, constraints on the spread of primary masses have been dominated by systematic uncertainties. The present correlation measurement is not affected by systematics in the measurement of the depth of shower maximum or the signal in the water Cherenkov stations. The analysis relies on general characteristics of air showers and is thus robust also with respect to uncertainties in hadronic event generators. The observed correlation in the energy range around the `ankle' at lg(E/eV)=18.519.0\lg(E/{\rm eV})=18.5-19.0 differs significantly from expectations for pure primary cosmic-ray compositions. A light composition made up of proton and helium only is equally inconsistent with observations. The data are explained well by a mixed composition including nuclei with mass A>4A > 4. Scenarios such as the proton dip model, with almost pure compositions, are thus disfavoured as the sole explanation of the ultrahigh-energy cosmic-ray flux at Earth.Comment: Published version. Added journal reference and DOI. Added Report Numbe

    Anisotropic flow of charged hadrons, pions and (anti-)protons measured at high transverse momentum in Pb-Pb collisions at sNN=2.76\sqrt{s_{\rm NN}}=2.76 TeV

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    The elliptic, v2v_2, triangular, v3v_3, and quadrangular, v4v_4, azimuthal anisotropic flow coefficients are measured for unidentified charged particles, pions and (anti-)protons in Pb-Pb collisions at sNN=2.76\sqrt{s_{\rm NN}} = 2.76 TeV with the ALICE detector at the Large Hadron Collider. Results obtained with the event plane and four-particle cumulant methods are reported for the pseudo-rapidity range η<0.8|\eta|<0.8 at different collision centralities and as a function of transverse momentum, pTp_{\rm T}, out to pT=20p_{\rm T}=20 GeV/cc. The observed non-zero elliptic and triangular flow depends only weakly on transverse momentum for pT>8p_{\rm T}>8 GeV/cc. The small pTp_{\rm T} dependence of the difference between elliptic flow results obtained from the event plane and four-particle cumulant methods suggests a common origin of flow fluctuations up to pT=8p_{\rm T}=8 GeV/cc. The magnitude of the (anti-)proton elliptic and triangular flow is larger than that of pions out to at least pT=8p_{\rm T}=8 GeV/cc indicating that the particle type dependence persists out to high pTp_{\rm T}.Comment: 16 pages, 5 captioned figures, authors from page 11, published version, figures at http://aliceinfo.cern.ch/ArtSubmission/node/186

    Centrality dependence of charged particle production at large transverse momentum in Pb-Pb collisions at sNN=2.76\sqrt{s_{\rm{NN}}} = 2.76 TeV

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    The inclusive transverse momentum (pTp_{\rm T}) distributions of primary charged particles are measured in the pseudo-rapidity range η<0.8|\eta|<0.8 as a function of event centrality in Pb-Pb collisions at sNN=2.76\sqrt{s_{\rm{NN}}}=2.76 TeV with ALICE at the LHC. The data are presented in the pTp_{\rm T} range 0.15<pT<500.15<p_{\rm T}<50 GeV/cc for nine centrality intervals from 70-80% to 0-5%. The Pb-Pb spectra are presented in terms of the nuclear modification factor RAAR_{\rm{AA}} using a pp reference spectrum measured at the same collision energy. We observe that the suppression of high-pTp_{\rm T} particles strongly depends on event centrality. In central collisions (0-5%) the yield is most suppressed with RAA0.13R_{\rm{AA}}\approx0.13 at pT=6p_{\rm T}=6-7 GeV/cc. Above pT=7p_{\rm T}=7 GeV/cc, there is a significant rise in the nuclear modification factor, which reaches RAA0.4R_{\rm{AA}} \approx0.4 for pT>30p_{\rm T}>30 GeV/cc. In peripheral collisions (70-80%), the suppression is weaker with RAA0.7R_{\rm{AA}} \approx 0.7 almost independently of pTp_{\rm T}. The measured nuclear modification factors are compared to other measurements and model calculations.Comment: 17 pages, 4 captioned figures, 2 tables, authors from page 12, published version, figures at http://aliceinfo.cern.ch/ArtSubmission/node/284

    The exposure of the hybrid detector of the Pierre Auger Observatory

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    The Pierre Auger Observatory is a detector for ultra-high energy cosmic rays. It consists of a surface array to measure secondary particles at ground level and a fluorescence detector to measure the development of air showers in the atmosphere above the array. The "hybrid" detection mode combines the information from the two subsystems. We describe the determination of the hybrid exposure for events observed by the fluorescence telescopes in coincidence with at least one water-Cherenkov detector of the surface array. A detailed knowledge of the time dependence of the detection operations is crucial for an accurate evaluation of the exposure. We discuss the relevance of monitoring data collected during operations, such as the status of the fluorescence detector, background light and atmospheric conditions, that are used in both simulation and reconstruction.Comment: Paper accepted by Astroparticle Physic
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